Patent GB-858865-A (GB)
Title: Fibers, films and the like of polymers of alkoxyalkyl vinyl or ª‡-methylvinyl sulfides
IPC: C08F8/00
Filed: 1957-05-28
Abstract: A fibre, film or like product having at least one small dimension of the order of one-tenth to twenty mils is made from a thermoplastic addition polymer derived from unsaturated molecules comprising at least 0,2% by weight (preferably 0,2 to 30%) of a vinyl thioether of formula:  CH2 = C(R) SR1 OR11 where R is hydrogen or a methyl group, R1 is a -CH2-, -CH(CH3)- or -C(CH3)2- group, and R11 is an alkyl group.  The polymer may be a homopolymer or a binary, ternary or quaternary copolymer and may have a molecular weight of 15,000 to 2,000,000 or more.  Specified copolymerizable monomers are ethylene; isobutylene, styrene, vinyl toluene, butadiene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl ethers, (e.g. the methyl ether), acrylamide, methacrylamide; acrylates, methacrylates and taconates of monohydric alcohols having 1-18 carbon atoms or of the mono-ethers of glycols; and vinyl esters (e.g. the propionate, butyrate and laurate). Polymerizatio may be effected by the bulk, solution, emulsion or suspension technique using a conventional free-radical catalyst. In the emulsion technique a conventional redox system is used together with an anionic, cationic or non-ionic emulsifying agent and, if desired, a polyvalent metal (e.g. iron), The fibres or films are normally subjected to hydrolysis to replace the -R1 OR11 groups with hydrogen atoms followed by treatment with a mild oxidizing agent (e.g. air, a dilute aqueous solution of hydrogen peroxide, chlorine sodium hypochlorite, calcium hypochlorite, nitric acid, potassium permanganate, peracetic acid, performic acid or potassium dichromate or an alcoholic solution of iodine) to effect cross-linking by disulphide linkages.  When an aqueous polymer dispersion is spun, a fusion-aid may be introduced before or after emulsion polymerization (e.g. an organic nitrile for copolymers based on acrylonitrile or methacrylonitrile or a hydrocarbon, a chlorinated hydrocarbon, ethylacetate or butylacetate for copolymers based on acrylates).  In Examples (1) A mixture of acrylonitrile, butoxyethyl acrylate and methoxymethyl vinyl sulphide is copolymerized in an aqueous medium containing (in addition to sulphuric acid and sodium hydroxide as pH adjusters) ferrous sulphate heptahydrate, ethylenediaminotetracetic acid, potassium laurate, sodium formaldehyde sulphoxylate dihydrate, methylsuccinonitrile (fusion-aid) and phenylcyclohexene peroxide dissolved in toluene.  In further examples copolymers of the following substances are similarly emulsion polymerized (2) and (3) Acrylonitrile, 3. 3. 5-trimethyl cyclohexylacrylate and methoxymethyl vinyl sulphide; (5) Butadiene, styrene and methoxymethyl vinyl sulphide; (6) Methyl methacrylate, butyl acrylate and CH2 =CHSCH (CH3) O CH3.  In a further example (4) A copolymer of vinylidene chloride, vinyl acetate and CH2 = C(CH3) SC (CH3)2 OC2H5 is prepared.  A copolymer of vinylacetate and methoxymethyl vinyl sulphide is also referred to.  The above polymers are made into filaments or films by a dry-or wet-spinning process by extruding a melt of the polymer, a solution of the polymer in water or an organic solvent (e.g. acetone, dioxane, methyl ethyl ketone, dimethyl formamide, dimethyl acetamide, acetonitrile or nitromethane), or an aqueous dispersion of the polymer.  In the dry-spinning of polymer melts, the polymer is preferably extruded into an atmosphere at 20 DEG -50 DEG C which is made oxygen-free to avoid cross-linking.  In the dry-spinning of polymer dispersions or solutions, the polymer is extruded into a heated atmosphere at 30 DEG -400 DEG C. (180 DEG -400 DEG C. in the case of aqueous dispersions) and, if this is insufficient to effect coalesence of polymer particles, the extruded products are thereafter heated to at least 30 DEG C. above their second order transition temperature.  In the wet-spinning process a solution or dispersion of the polymer is extruded into a liquid coagulating bath which may be (a) of pH 1-6 provided by an acid (e,g. sulphuric, hydrochloric phosphoric, boric, sulphamic, oxalic, formic, acetic, citric, lactic, ethanesulphonic or toluenesulphonic acid) and, possibly, a buffer (e.g. sodium dihydrogen phosphate) or a polyvalent metal salt (e.g. a sulphate or chloride of iron, aluminium, zirconium, tin, cobalt, nickel or zinc); (b) of pH 8-13 and made up of an electrolyte (e.g. a chloride, sulphate, formate, or hydroxide of potassium or sodium, or lithium chloride) and, possibly, a quaternary ammonium hydroxide or an organic material (e.g. urea or glucose); (c) of acidic, neutral or alkaline pH and made up of an aqueous solution of the sulphite, chloride, carbonate, bisulphite, acetate or borate of sodium, or of ammonium chloride or aluminium chloride. After leaving the coagulating bath the extruded products are normally neutralized and then washed with water or an organic liquid.  The extruded products, however they are made, are stretched, hydrolysed (if they have not already been so in an acid coagulating bath) and then cross-linked by treatment with an oxidizing agent (see above paragraph).  In Examples (1), (5) and (6) the polymer dispersions of examples 1, 5 and 6 (above) are spun into aqueous sodium bisulphite solution and the resulting filaments washed, fuse-dried at 260 DEG C., heat stretched at 140 DEG C. about 600% treated with aqueous phosphoric acid solution, treated with alcoholic iodine solution, washed and cured by heating at constant length at 150 DEG C.; (2) The polymer dispersion of example 2 is concentrated, extruded into a chamber containing dry air at 200 DEG C. and the resulting filaments heated to 280 DEG C. to fuse the particles, heat stretched at 130 DEG C., treated with aqueous phosphoric acid solution and then treated with sodium hypochlorite solution; (3) (7), (8) and (9).  The polymers dispersions of Examples 3, 7, 8 and 9 are spun into a phosphoric acid solution and the resulting filaments are washed in hot water, fuse dried at 200 DEG C., stretched 800% at 100 DEG C., possibly treated with aqueous phosphoric acid and then treated with alcoholic iodine solution and after removal of excess iodine heated at 130 DEG -150 DEG C. whilst allowing 5% relaxation; (4) An acetone solution of the polymer of example 4 is extruded downwardly into a countercurrent flow of heated air and the resulting filaments stretched 80%, treated with aqueous phosphoric acid, treated with aqueous hydrogen peroxide and after removal of excess solution heated at 110 DEG C. Specifications 826,659 and 858,864 are referred to.ALSO:Fabrics made from fibres of polymers or copolymers of vinyl thioethers of formula: CH2=C(R)SR1OR11 where R is hydrogen or a methyl group, R1 is a -CH2-, -CH(CH3)- or -C(CH3)2 and R11 is an alkyl group are shrink-proofed by first treating them with an acid to replace -R1OR11 groups in the polymer with hydrogen atoms and then treating the fabrics with a mild oxidising agent to effect cross-linking of the polymer by disulphide linkages.  In Example 10, a filament made from a copolymer of acrylonitrile, butoxyethyl acrylate and methoxy vinyl sulphide was heat stretched, cut to staple fibre and woven into a fabric which was treated first with phosphoric acid and then with iodine and finally heated while held against shrinkage in a tenter frame at 150 DEG C. Specifications 826,659 and 858,864 are referred to.